Substituted 2-pyrimidinyl-acetic acid derivatives, and their use as herbicides, fungicides and plant growth regulators

ABSTRACT

The invention relates to new 2-pyrimidinyl- and 2-triazinylacetic acid derivatives of general formula I ##STR1## in which A, R 2-5  and X have the meanings given in the description, processes for their preparation and their use as herbicides, fungicides and plant growth regulants.

This is division of application Ser. No. 07/590,675, filed Oct. 1, 1990, and now U.S. Pat. No. 5,098,465.

This invention relates to new substituted 2-pyrimidinyl- and 2-triazinylacetic acid derivatives, processes for their preparation and their use as herbicides, fungicides and plant growth regulators.

It is known that pyrimidine derivatives possess herbicidal activity (EP 223 406, 249 707, 249 708, 287 072 and 287 079). However, the herbicidal activity of these known compounds is often insufficient or selectivity problems are seen in important crops.

The object of the present invention is to make new compounds that do not have these disadvantages and have improved biological properties over the known compounds.

It has now been found that substituted 2-pyrimidinyl- and 2-triazinylacetic acid derivatives of general formula I ##STR2## in which A is one of the groups --CO--OR¹, --CO--NR⁶ R⁷ or --C≡N,

R¹ is hydrogen, C₁ -C₁₂ -alkyl (optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, tri-C₁ -C₄ -alkylammoniumhalide, C₂ -C₅ -alkylenimino or di-C₁ -C₄ -alkylmethyleniminooxy), C₂ -C₁₂ -alkyl, interrupted by one or more oxygen or sulphur atoms and optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino, a C₃ -C₈ -alkenyl or C₃ -C₈ -alkynyl group (each of which is optionally substituted by C₃ -C₈ -alkoxy, phenyl or halogen), C₃ -C₈ -cycloalkyl, optionally substituted by methyl, di-C₁ -C₄ -alkylmethylenimino or C₃ -C₆ -cycloalkylenimino;

R² and R³, which may be the same or different, are C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino or halogen;

R⁴ is hydrogen, C₁ -C₁₀ -alkyl (optionally substituted by one or more of the same or different C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, halogen, phenyl or halophenyl), a C₂ -C₁₀ -alkenyl or C₂ -C₁₀ -alkynyl group (each of which is optionally substituted by one or more of the same or different C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, halogen or phenyl), or a C₃ -C₈ -cycloalkyl or C₄ -C₈ -cycloalkenyl group (each of which is optionally substituted by one or more of the same or different C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, trifluoromethyl, halogen or phenyl);

R⁵ has the same meaning as R⁴ except hydrogen; or

R⁴ and R⁵ together with the carbon to which they are attached form a C₃ -C₈ -cycloalkyl group;

R⁶ and R⁷, which may be the same or different, are hydrogen or C₁ -C₄ -alkyl;

X is methine or nitrogen,

with the provisos,

a) A is not --C≡N, when R⁴ and/or R⁵ are methyl or benzyl,

b) R¹ is not ethyl, when R⁴ is hydrogen and R⁵ is benzyl, and

c) R⁵ is not ethyl or allyl, when R¹ is hydrogen, R² and R³ are each chlorine and X is nitrogen;

as well as their alkali metal, alkaline earth metal, ammonium and organic ammonium salts, and their optically active isomers, show interesting herbicidal, fungicidal and plant growth regulant activity.

The expression "halogen" means fluorine, chlorine, bromine and iodine. By the term alkali metal is meant lithium, sodium or potassium and by the term alkaline earth metal is meant calcium, strontium or barium.

The compounds of the invention of general formula I can be

A) by reacting a compound of general formula II ##STR3## in which R², R³ and X have the meanings given under general formula I, and Y is leaving group, such as halogen, alkylsulphonyl or phenylsulphonyl, with a compound of general formula III ##STR4## in which A, R⁴ and R⁵ have the meanings given under general formula I, in a suitable solvent in the presence of a suitable base, or

B) by reacting a compound of general formula IV ##STR5## in which R¹, R², R³, R⁴, R⁵ and X have the meanings given under general formula I, except for X being hydrogen, with an alkali metal base or alkaline earth metal base, in a suitable polar solvent, to give a compound of general formula V ##STR6## in which R², R³, R⁴, R⁵ and X have the meanings given under general formula I and M1 is an alkali metal atom or an equivalent of an alkaline earth metal atom, and optionally base, in a suitable polar in which A, R⁴ and R⁵ have the meanings given under general formula I, in a suitable solvent in the presence of a suitable base, or

C) by reacting a compound of general formula V ##STR7## in which R², R³, R⁴, R⁵, M¹ and X have the meanings in a suitable solvent, to give a compound of general formula VI ##STR8## in which R², R³, R⁴, R⁵ and X have the meanings given under general formula I, or

D) by reacting a compound of general formula VI ##STR9## in which R², R³, R⁴, R⁵ and X have the meanings given under general formula I, with a suitable base, in a formula VII ##STR10## in which R², R³, R⁴, R⁵ and X have the meanings given under general formula I and M² is an alkali metal atom or an equivalent of an alkaline earth metal atom, an ammonium ion or an organic ammonium group, or

E) by reacting a compound of general formula VIII ##STR11## in which A, R², R³, R⁴ and X have the meanings given under general formula I, with a compound of general of formula IX

    R.sup.5 --Z                                                (IX)

in which R⁵ has the meaning given under general formula I, and Z is a leaving group, such as halogen, alkylsulphonyl, phenylsulphonyl or alkoxysulphonyloxy, in a suitable solvent, in the presence of a suitable base.

The individual process variants are preferably carried out in the presence of a diluent. For this, a solvent which is inert to the reactants is used.

Suitable solvents include water, aliphatic, alicyclic and aromatic hydrocarbons, that can be optionally chlorinated, such as for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethane, ethers, such as for example diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; ketones, such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone, nitriles, such as for example acetonitrile and propionitrile, alcohols, such as for example methanol, ethanol, isopropanol, butanol and ethylene glycol, esters, such as for example ethyl acetate and amyl acetate, amides, such as for example dimethylformamide and dimethylacetamide, sulphones and sulphoxides, such as for example dimethyl sulphoxide, and bases, such as for example pyridine.

The presence of a catalyst can be an advantage. Suitable catalysts include potassium iodide and onium compounds. such as quaternary ammonium, phosphonium and arsonium compounds as well as sulphonium compounds. Also suitable are polyglycol ethers, especially cyclic ethers, such as 18-crown-6, and tertiary amines, such as for example tributylamine. Preferred compounds are quaternary ammonium compounds, such as for example benzyltriethylammonium chloride and tetrabutylammonium bromide.

The reactions can be carried out under atmospheric pressure but if desired higher or lower pressures can be used.

The process variant A) is preferably carried out in an aprotic solvent such as benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, dimethylformamide or dimethyl sulphoxide.

Bases that can be used include sodium hydride, potassium tert-butylate or lithium diisopropylamide.

The reactions are suitably carried out between -78° C. and the boiling point of the particular solvent or solvent mixture.

The reaction usually takes 5 minutes to 48 hours, preferably 0.5 to 24 hours.

Compounds of general formula II are described in the literature or can be prepared by methods analogous to those described in the literature.

For the processes variants B) and C), there is preferably used as a solvent an alcohol, such as ethanol, propanol or isopropanol, a ketone, such as acetone or methyl ethyl ketone, dimethylformamide or dimethyl sulphoxide, water or a polar solvent/water mixture.

Bases that can be used include for example, carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate, or metal hydroxides, such as sodium hydroxide or potassium hydroxide.

The reaction temperature lies between room temperature and the boiling point of the particular solvent. The reaction time lies between 0.5 to 36 hours.

When R¹ in general formula IV is benzyl, a catalytic reduction (hydrogenation) of the compound of formula VI can also be used.

Suitable solvents for process variant D) include hydrocarbons, such as benzene, toluene or xylene, halogenated hydrocarbons, such as methylene chloride or chloroform, alcohols, such as methanol, ethanol or isopropanol, ethers, such as for example diethyl ether, diisopropyl ether, tetrahydrofuran or 1,4-dioxane, ketones, such as acetone or methyl ethyl ketone, esters, such as methyl acetate or ethyl acetate, or nitriles, such as acetonitrile.

Bases that can be used include an alkali metal, such as sodium or potassium, an alkali metal or alkaline earth metal hydride, such as sodium hydride, potassium hydride or calcium hydride, a carbonate, such as sodium carbonate, potassium carbonate or calcium carbonate, or a metal hydroxide, such as sodium hydroxide or potassium hydroxide. Organic ammonium bases that can be used include for example, ammonia an alkylamine (primary amine), a dialkylamine (secondary amine) or a trialkylamine (tertiary amine).

The temperature of the reaction falls within room temperature and the boiling point of the particular solvent or solvent mixture. The reaction time lies between 5 minutes and 10 hours.

The process variant E) is preferably carried out in an aprotic solvent, such as benzene, toluene, xylene, tetrahydrofuran, diethyl ether, hexane, dimethylformamide or dimethyl sulphoxide.

Bases that can be used include for example sodium hydride, potassium tert-butylate or lithium diisopropylamide.

The temperature of the reaction lies between -78° C. and the boiling point of the particular solvent or solvent mixture.

The reaction time lies between 1 and 24 hours.

The compounds of the invention prepared by these processes can be isolated from the reaction mixtures in conventional manner, for example by distillation of the solvent at normal or reduced pressure, by precipitation with water or by extraction.

A higher level of purity can be achieved as a rule by column chromatography as well as by fractional distillation or crystallisation.

The compounds of the invention are, as a rule, colourless and odourless liquids or crystals that are soluble in water, slightly soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane and highly soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons, such as benzene, toluene and xylene, ethers, such as diethyl ether, tetrahydrofuran and dioxane, nitriles, such as acetonitrile, alcohols, such as methanol and ethanol, amides, such as dimethylformamide, and sulphoxides, such as dimethyl sulphoxide.

The compounds of the invention show a good herbicidal activity in broad leaved weeds and grasses. A selective use in various crops is possible, for example in such as rape, beets, soya beans, cotton, rice, barley, wheat and other cereals. Individual active substances are particularly suitable as selective herbicides in beet, cotton, soya and cereals. However the compounds can be used for control of weeds in permanent crops, such as for example forestry, ornamental trees, fruit, vine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations and for the selective control of weeds in annual crops.

The compounds of the invention can used for example against the following plant species:

Dicotyledonous weeds of the species Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

Monocotyledonous weeds of the species Avena, Alopecurus, Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis, Ischaemum and Apera.

The rates of use vary depending on the manner of pre- and postemergent use between 0.001 and 5 kg/ha.

The compounds of the invention can also be used as defoliants, desiccants and as total herbicides. They also influence plant growth and can thus be used to influence plant growth of crops. Some compounds also show fungicidal activity.

The compounds of the invention can be used either alone or in admixture with one another or with other active agents. Optionally, other plant-protective agents or pesticides can be added, depending on the purpose for the treatment. When it is desired to broaden the spectrum of activity, other herbicides can also be added. Herbicidally active mixing partners suitable in this connection include for example, the active agents listed in Weed Abstracts, vol. 38, No.3 (1989) under the heading "Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".

An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose.

The designated active ingredients or their mixtures can suitably be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants.

Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oil fractions and plant oils.

Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talc, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.

As surface-active agents there can be used for example calcium lignosulphonate, polyoxyethylenealkylphenyl ethers, naphthalenesulphonic acids and their salts, phenolsulphonic acids and their salts, formaldehyde condensates, fatty alcohol sulphates, as well as substituted benzenesulphonic acids and their salts.

The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.

The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 1,000 1/ha. The agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.

The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.

Formulations can be prepared, for example, from the following ingredients.

A) Wettable Powder

1) 25 percent by weight active ingredient

60 percent by weight kaolin

10 percent by weight silicic acid

5 percent by weight of a mixture of calcium lignosulphonate and the sodium salt of N-methyl-N-oleyltaurine

2) 40 percent by weight active ingredient

25 percent by weight bentonite

25 percent by weight colloidal silicic acid

10 percent by weight of a mixture of calcium lignosulphonate and alkylphenyl polyglycol ether

B) Paste

45 percent by weight active ingredient

5 percent by weight sodium aluminium silicate

15 percent by weight cetyl polyglycol ether with 8 mol of ethylene oxide

2 percent by weight spindle oil

10 percent by weight polyethylene glycol

23 percent by weight water

C) Emusifiable Concentrate

25 percent by weight active ingredient

15 percent by weight cyclohexanone

55 percent by weight xylene

5 percent by weight of a mixture of calcium dodecylbenzenesulphonate and nonylphenolpolyoxyethylene.

The following Examples illustrate the preparation of compounds of the invention.

EXAMPLE 1 Ethyl 2-(4,6-dimethoxypyrimidin-2-yl)pentanoate

4,2 g (30 mmol) Diisopropylamine in 100 ml tetrahydrofuran, under nitrogen at -78° C., was treated with 19 ml (30 mmol) 1.6M butyllithium in hexane. The mixture was stirred for 30 minutes and then at -60° C., a solution of 3.5 g (27 mmol) ethyl pentanoate, dissolved in 20 ml tetrahydrofuran, was added dropwise. The mixture was stirred for a further hour and 5.9 g (27 mmol) 4,6-dimethoxy-2-methylsulphonylpyrimidine was added, portionwise. The temperature of the mixture rose over 2 hours to +10° C. The reaction mixture was then washed with saturated aqueous ammonium chloride and sodium chloride. The aqueous phase was extracted with ethyl acetate. The organic phases were dried over magnesium sulphate and concentrated. The resulting yellow oil was finally purified on silica gel using a hexane/ethyl acetate mixture (0 to 20% ethyl acetate).

Yield: 3.2 g =42% of theory

n²⁰ _(D) : 1.4824

EXAMPLE 2 2-(4,6-Dimethoxypyrimidin-2-yl)pentanoic acid

A mixture of 2.2 g (8 mmol) ethyl 2-(4,6-dimethoxypyrimidin-2-yl)pentanoate in 20 ml methanol and 3 ml 5N caustic soda was stirred overnight at room temperature. The mixture was concentrated and the residue dissolved in 10 ml water, extracted with 50 ml ethyl acetate and the aqueous phase acidified with 2N hydrochloric acid until it was pH 5. The aqueous phase was extracted three times with ether, the combined phases were dried over magnesium sulphate and concentrated.

Yield: 1.7 g=85% of theory

mp: 71°-73° C. (dec.)

EXAMPLE 3 Methyl 2,4-dimethyl-2-(4,6-dimethoxy-s-triazin-2-yl)pentanoate

0.5 g (17 mmol) Sodium hydride (80% in oil) was added at room temperature, under nitrogen, to a solution of 3.96 g (14 mmol) methyl 2-(4,6-dimethoxy-s-triazin-2-yl)pentanoate in 35 ml dimethylformamide. The mixture was stirred for one hour at room temperature and then 2.0 g (16 mmol) dimethyl sulphate was added dropwise. The mixture was left for 2.5 hours at room temperature, then added to 200 ml water and extracted twice with ethyl acetate. The combined organic phase was washed with saturated aqueous sodium chloride, dried over magnesium sulphate and concentrated. The crude product was purified by silica gel chromatography using a hexane/ethyl acetate mixture (0 to 20% ethyl acetate).

Yield: 2.3 g =62% of theory

n²⁰ _(D) : 1.4775

In a similar manner the following compounds were prepared

    __________________________________________________________________________      ##STR12##                                                                     Example                                                Physical                No   R.sup.1        R.sup.2                                                                               R.sup.3                                                                               R.sup.4 R.sup.5   X  constant                __________________________________________________________________________      4   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4794                   5   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH mp:                                                                            109-110°                                                                C.                                                                             (dec.)                   6   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       Cyclohexyl                                                                               CH n.sub.D.sup.20 :                                                               1.5028                   7   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       Cyclohexyl                                                                               CH n.sub.D.sup.20 :                                                               1.4982                   8   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       Cyclohexyl                                                                               CH mp: 88-89°                                                              C.                                                                             (dec.)                   9   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       C(CH.sub.3).sub.3                                                                        CH n.sub.D.sup. 20 :                                                              1.4868                  10   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.4 CH.sub.3                                                                CH n.sub.D.sup.20 :                                                               1.4755                  11   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.4 CH.sub.3                                                                CH n.sub.D.sup.20 :                                                               1.4920                  12   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.2 SCH.sub.3                                                               CH n.sub.D.sup.20 :                                                               1.5175                  13   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH(CH.sub.3).sub.2                                                              CH n.sub.D.sup.20 :                                                               1.4773                  14   CH.sub.2 CH.sub.3                                                                             Cl     OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4926                  15   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4796                  16   CH.sub.2 CH.sub.3                                                                             CH.sub.3                                                                              CH.sub.3                                                                              H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4803                  17   CH.sub.2 CH.sub.3                                                                             CH.sub.3                                                                              CF.sub.3                                                                              H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4406                  18   CH.sub.2 CH.sub.3                                                                             CH.sub.3                                                                              OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4794                  19   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             CH.sub.3                                                                               (CH.sub.2).sub.2 CH.sub.3                                                                CH n.sub.D.sup.20 :                                                               1.4829                  20   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH(CH.sub.3).sub.2                                                              N  n.sub.D.sup.20 :                                                               1.4740                  21   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.3  CH n.sub.D.sup.20 :                                                               1.4808                  22   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2)CH.sub.3                                                                       CH n.sub.D.sup.20 :                                                               1.4834                  23   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4834                  24   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       C(CH.sub.3).sub.3                                                                        N  mp: 82-83°                                                              C.                                                                             (dec.)                  25   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CHCH.sub.2                                                                      N  n.sub.D.sup.20 :                                                               1.4966                  26   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CHCH.sub.2                                                                      N  n.sub.D.sup.20 :                                                               1.4882                  27   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CHCH.sub.2                                                                      N  mp: 71-73°                                                              C.                      28   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH(CH.sub.3).sub.2                                                              N  mp: 86-88°                                                              C.                      29   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.2 C CH                                                                    N  n.sub.D.sup.20 :                                                               1.4903                  30   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.2 CCH                                                                     N  mp: 73-75°                                                              C.                                                                             (dec.)                  31   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4815                  32   CH.sub.2 (CH.sub.3).sub.2                                                                     OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4744                  33   Tetrahydrofurfuryl                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4946                  34   CH.sub.2 CCH   OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4922                  35   CH.sub.2 CHC(CH.sub.3)CCH                                                                     OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.5021                  36   H.sub.3 NCH(CH.sub.3).sub.2                                                                   OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  mp: 127°                                                                C.                                                                             (dec.)                  37   NC(CH.sub.3).sub.2                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4895                  38   CH.sub.2 OCH.sub.3                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4782                  39   CH.sub.2 CCH   OCH.sub.3                                                                             OCH.sub.3                                                                             H       C(CH.sub.3).sub.3                                                                        N  mp: 72-74°                                                              C.                                                                             (dec.)                  40   CH.sub.2 CHC(CH.sub.3)CCH                                                                     OCH.sub.3                                                                             OCH.sub.3                                                                             H       C(CH.sub.3).sub.3                                                                        N  n.sub.D.sup.20 :                                                               1.5049                  41   CH.sub.3       OCH.sub.3                                                                             N(CH.sub.3).sub.2                                                                     H       CH(CH.sub.3).sub.2                                                                       N  mp: 46° C.       42   CH.sub.3       CH.sub.2 OCH.sub.3                                                                    OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4805                  43   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             (CH.sub.2).sub.5  CH n.sub.D.sup.20 :                                                               1.5056                  44   H              OCH.sub.3                                                                             OCH.sub.3                                                                             (CH.sub.2).sub.5  CH mp: 88-90°                                                              C.                      45   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             (CH.sub.2).sub.3  CH n.sub.D.sup.20 :                                                               1.4928                  46   H              OCH.sub.3                                                                             OCH.sub.3                                                                             (CH.sub.2).sub.3  CH mp:                                                                            120-121°                                                                C.                                                                             (dec.)                  47   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             CH.sub.2                                                                               CH.sub.2 CH(CH.sub.3).sub.2                                                              N  n.sub.D.sup.20 :                                                               1.4856                                                    CHCH.sub.2                                   48   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.3 CH.sub.3                                                                N  n.sub.D.sup.20 :                                                               1.4716                  49   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH(CH.sub.3).sub.2                                                              N  n.sub.D.sup.20 :                                                               1.4794                  50   H              OCH.sub.3                                                                             OCH.sub.3                                                                             CH.sub.3                                                                               (CH.sub.2).sub.2 CH.sub.3                                                                CH mp: 68-70°                                                              C.                      51   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             CH.sub.3                                                                               CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4813                  52   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             CH.sub.3                                                                               CH.sub.2 CHCH.sub.2                                                                      CH n.sub.D.sup.20 :                                                               1.4884                  53   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.3 CH.sub.3                                                                CH n.sub.D.sup.20 :                                                               1.3769                  54   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.3 CH.sub.3                                                                CH n.sub.D.sup.20 :                                                               1.4781                  55   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.3 CH.sub.3                                                                CH mp: 71-72°                                                              C.                      56   NC(CH.sub.3).sub.2                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.3 CH.sub.3                                                                CH n.sub.D.sup.20 :                                                               1.4972                  57   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             CH.sub.2CCH                                                                            CH.sub.2 CCH                                                                             CH mp: 70-73°                                                              C.                      58   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.2 CH.sub.3                                                                N  n.sub.D.sup.20 :                                                               1.4844                  59   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       Cyclopropylmethyl                                                                        CH n.sub.D.sup.20 :                                                               1.4973                  60   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                            CH n.sub.D.sup.20 :                                                               1.4846                  61   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                            CH n.sub.D.sup.20 :                                                               1.4796                  62   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                            N  n.sub. D.sup.20 :                                                              1.4864                  63   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                            N  n.sub.D.sup.20 :                                                               1.4777                  64   Tetrahydrofurfuryl                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4903                  65   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.3  CH mp: 79°C.                                                               (dec.)                  66   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH.sub.3                                                                        CH n.sub.D.sup.20 :                                                               1.4816                  67   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH.sub.3                                                                        CH n.sub.D.sup.20 :                                                               1.4807                  68   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                            CH mp: 82° C.                                                              (dec.)                  69   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CH.sub.3                                                                        CH mp: 97° C.                                                              (dec.)                  70   NC(CH.sub.3).sub.2                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3)CH.sub.2 CH.sub.3                                                            CH mp: 124°                                                                C.                                                                             (dec.)                  71   NC(CH.sub.3).sub.2                                                                            OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2 ).sub.2 CH.sub.3                                                               CH n.sub.D.sup.20 :                                                               1.4974                  72   NC(CH.sub.3)CH.sub.2 CH.sub.3                                                                 OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4946                  73   Benzyl         OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.5226                  74   Benzyl         OCH.sub.3                                                                             Cl     H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.5351                  75   (CH.sub.2).sub.2 ONC(CH.sub.3).sub.2                                                          OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4852                  76   CH.sub.2 CH.sub.3                                                                             OCH.sub.2 CH.sub.3                                                                    OCH.sub.2 CH.sub.3                                                                    H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4758                  77   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             Cl     H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4891                  78   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             (CH.sub.2).sub.3 CH.sub.3                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4685                  79   (CH.sub.2).sub.2N(CH.sub.3).sub.2                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4850                  80   (CH.sub.2).sub.2N(CH.sub.2).sub.5                                                             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3 ).sub.2                                                                      N  n.sub.D.sup.20 :                                                               1.4967                  81   (CH.sub.2).sub.3 CH.sub.3                                                                     OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4763                  82   (CH.sub.2).sub.2 OCH.sub.2 CH.sub.3                                                           OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4755                  83   (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OCH.sub.2 CH.sub.3                                         OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4759                  84   (CH.sub.2).sub.2 O-benzyl                                                                     OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.5166                  85   (CH.sub.2).sub.2 OH                                                                           OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4972                  86   CH.sub.2 CO.sub.2 H                                                                           OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N                          87   CH.sub.2 CO.sub.2 CH.sub.3                                                                    OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N                          88   H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       1-Methylbenzyl                                                                           CH mp: 141°                                                                C.                                                                             (dec.)                  89   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       1-Methylbenzyl                                                                           CH mp: 81° C.       90   CH.sub.2 CH.sub.3                                                                             OCH.sub.2 CH.sub.3                                                                    OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4732                  91   CH.sub.2 CO.sub.2 CH.sub.3                                                                    OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4859                  92   CH(CH.sub.3)CO.sub.2 CH.sub.3                                                                 OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4809                  93   (CH.sub.2).sub.2N(CH.sub.3).sub.3 J                                                           OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  mp: 74-76°                                                              C.                      94   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH.sub.2 CH.sub.3                                                                    H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4746                  95   CH.sub.2 CH.sub.3                                                                             CH.sub.3                                                                              OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4773                  96   CH.sub.2 CH.sub.3                                                                             OCH.sub.3                                                                             OCH(CH.sub.3).sub.2                                                                   H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4724                  97   CH.sub.2 CH.sub.3                                                                             OCH(CH.sub.3).sub.2                                                                   OCH(CH.sub.3).sub.2                                                                   H       CH(CH.sub.3).sub.2                                                                       N  n.sub.D.sup.20 :                                                               1.4688                  98   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       Benzyl    CH n.sub.D.sup.24 :                                                               1.5350                  99   CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             Benzyl  Benzyl    CH mp:                                                                            107-109°                                                                C.                      100  H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       Benzyl    CH mp:                                                                            100-104°                                                                C.                      101  CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             3-Chlorobenzyl                                                                         3-Chllorobenzyl                                                                          CH n.sub.D.sup.20 :                                                               1.5660                  102  CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       3-Chlorobenzyl                                                                           CH n.sub.D.sup.24 :                                                               1.5410                  103  CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             4-Chlorobenzyl                                                                         4-Chlorobenzyl                                                                           CH mp:                                                                            122-125°                                                                C.                      104  H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       3-Chlorobenzyl                                                                           CH mp:                                                                            117-118°                                                                C.                      105  CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       4-Chlorobenzyl                                                                           CH mp: 66-68°                                                              C.                      106  H              OCH.sub.3                                                                             OCH.sub.3                                                                             H       4-Chlorobenzyl                                                                           CH mp:                                                                            103-104°                                                                C.                      107  CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             (CH.sub.2).sub.3 CH.sub.3                                                              (CH.sub.2).sub.3 CH.sub.3                                                                CH n.sub.D.sup.24 :                                                               1.4780                  108  CH.sub.3       OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH.sub.2 CCH                                                                             CH n.sub.D.sup.24 :                                                               1.5020                  109  (CH.sub.2).sub.3CO.sub.2 CH.sub.2 CH.sub.3                                                    OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4768                  __________________________________________________________________________      ##STR13##                                                                     Example                                                                        No   A              R.sup.2                                                                               R.sup.3                                                                               R.sup.4 R.sup.5   X  constant                __________________________________________________________________________     110  CN             OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4930                  111  CONH.sub.2     OCH.sub.3                                                                             OCH.sub.3                                                                             H       (CH.sub.2).sub.3 CH.sub.3                                                                CH mp: 75-76°                                                              C.                      112  CONH.sub.2     OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH mp:                                                                            103-105°                                                                C.                      113  CON(CH.sub.3).sub.2                                                                           OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.5030                  114  CON(C.sub.2 H.sub.5).sub.2                                                                    OCH.sub.3                                                                             OCH.sub.3                                                                             H       CH(CH.sub.3).sub.2                                                                       CH n.sub.D.sup.20 :                                                               1.4960                  __________________________________________________________________________

The following examples illustrate the possibilities for use of the compounds of the invention.

EXAMPLE A

In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds of the invention, at a rate of 0.3 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the soil as emulsions or suspensions in 500 liters water/ha. Three weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show similar high efficacy.

In the following table:

    ______________________________________                                                0 =     no damage                                                              1 =     1-24% damage                                                           2 =     25-74% damage                                                          3 =     75-89% damage                                                          4 =     90-100% damage                                                         AGRRE = Elymus repens                                                          BROTE = Bromus tectorum                                                        SORHA = Sorghum halepense                                                      ABUTH = Abutilon theophrasti                                                   IPOSS = Ipomoea purpurea                                                       SEBEX = Sesbania exaltata                                               ______________________________________                                    

    ______________________________________                                                       A     B       S   A     I   S                                                  G     R       O   B     P   E                                                  R     O       R   U     O   B                                    Compound      R     T       H   T     S   E                                    of the invention                                                                             E     E       A   H     S   X                                    ______________________________________                                         Example 5     3     4       3   3     3   3                                    Example 15    3     4       3   3     3   3                                    Example 23    3     4       3   --    3   3                                    Example 33    3     3       3   2     2   2                                    Example 36    3     4       4   3     2   3                                    Example 62    3     4       3   --    --  2                                    Example 63    3     3       3   3     --  3                                    Example 64    3     3       3   3     2   3                                    Example 70    3     4       3   4     3   3                                    Example 72    3     4       3   3     2   3                                    Example 73    3     4       3   4     2   3                                    Untreated     0     0       0   0     0   0                                    Comparison                                                                     Imazamethabenz                                                                               1     2       2   2     2   1                                    ______________________________________                                    

EXAMPLE B

In a greenhouse, the noted plant species were treated post-emergently with the noted compounds of the invention, at a rate of 0.1 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the plants as emulsions or suspensions in 500 liters water/ha. Two weeks after the treatment, the compounds of the invention showed a high crop selectivity in wheat and maize with excellent activity against the weeds. The comparison material did not show similar high efficacy.

In the following table:

    ______________________________________                                                0 =      no damage                                                             l =      1-24% damage                                                          2 =      25-74% damage                                                         3 =      75-89% damage                                                         4 =      90-100% damage                                                        GLMXA =  Glycine maxima                                                        GOSHI =  Gossypium hirsutum                                                    HELAN =  Helianthus annuus                                                     TRZAX =  Triticum aestivum                                                     BROTE =  Bromus tectorum                                                       GALAP =  Galium aparine                                                        VERPE =  Veronica persica                                                      VIOSS =  Viola sp                                                       ______________________________________                                    

    ______________________________________                                                    G     G       H   T   B     G   V   V                                          L     O       E   R   R     A   E   I                                          X     S       L   Z   O     L   R   O                               Compound   M     H       A   A   T     A   P   S                               of the invention                                                                          A     I       N   X   E     P   E   S                               ______________________________________                                         Example 5  0     0       0   1   3     3   3   3                               Untreated  0     0       0   0   0     0   0   0                               Comparison                                                                     Imazamethabenz                                                                            0     1       1   0   0     1   2   1                               ______________________________________                                    

EXAMPLE C

In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds of the invention, at a rate of 0.3 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the soil as emulsions or suspensions in 500 liters water/ha. Three weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show similar high efficacy.

In the following table:

    ______________________________________                                                0 =      no damage                                                             1 =      1-24% damage                                                          2 =      25-74% damage                                                         3 =      75-89% damage                                                         4 =      90-100% damage                                                        GLMXA =  Glycine maxima                                                        GOSHI =  Gossypium hirsutum                                                    HELAN =  Helianthus annuus                                                     BROTE =  Bromus tectorum                                                       PANSS =  Panicum maximum                                                ______________________________________                                    

    ______________________________________                                                      G        G     H       B   P                                                   L        O     E       R   A                                                   X        S     L       O   N                                      Compound     M        H     A       T   S                                      of the invention                                                                            A        I     N       E   S                                      ______________________________________                                         Example 4    0        0     0       3   3                                      Example 8    1        1     1       3   3                                      Example 20   1        --    0       3   3                                      Example 31   0        0     1       3   3                                      Example 32   0        1     1       --  3                                      Example 34   0        --    1       3   3                                      Example 35   0        --    0       3   3                                      Example 37   0        0     0       3   3                                      Example 38   --       --    1       3   3                                      Example 60   1        0     0       3   3                                      Example 61   0        0     0       3   3                                      Example 68   1        1     1       --  3                                      Example 71   --       1     1       3   3                                      Example 75   0        --    1       3   3                                      Untreated    0        0     0       0   0                                      Comparison                                                                     Imazamethabenz                                                                              1        0     0       0   1                                      ______________________________________                                    

EXAMPLE D

In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds of the invention, at a rate of 0.1 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the soil as emulsions or suspensions in 500 liters water/ha. Three weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show similar high efficacy.

In the following table:

    ______________________________________                                                 0 =     no damage                                                              1 =     1-24% damage                                                           2 =     25-74% damage                                                          3 =     75-89% damage                                                          4 =     90-100% damage                                                         TRZAX = Triticum aestivum                                                      VERPE = Veronica persica                                                       VIOSS = Viola sp                                                       ______________________________________                                    

    ______________________________________                                                       T           V     V                                                            R           E     I                                                            Z           R     O                                              Compound      A           P     S                                              of the invention                                                                             X           E     S                                              ______________________________________                                         Example 22    0           3     3                                              Untreated     0           0     0                                              Comparison                                                                     Imazamethabenz                                                                               0           1     2                                              ______________________________________                                    

EXAMPLE E

In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds of the invention, at a rate of 1.0 kg active ingredient/ha. The compounds of the invention were sprayed evenly over the soil as emulsions or suspensions in 500 liters water/ha. Three weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show similar high efficacy.

In the following table:

    ______________________________________                                         0 =            no damage                                                       1 =            1-24% damage                                                    2 =            25-74% damage                                                   3 =            75-89% damage                                                   4 =            90-100% damage                                                  GLMXA =        Glycine maxima                                                  GOSHI =        Gossypium hirsutum                                              ZEAMX =        Zea mays                                                        BROTE =        Bromus tectorum                                                 SETVI =        Setaria viridis                                                 GALAP =        Galium aparine                                                  MATCH =        Matricaria chamomilla                                           VERPE =        Veronica persica                                                VIOSS =        Viola sp                                                        ______________________________________                                    

    ______________________________________                                                    G      G     Z    B   S    G   M    V   V                                      L      O     E    R   E    A   A    E   I                                      X      S     A    O   T    L   T    R   O                           Compound   M      H     M    T   V    A   C    P   S                           of the invention                                                                          A      I     X    E   I    P   H    E   S                           ______________________________________                                         Example 24 0      0     0    3   3    3   3    3   3                           Example 59 0      1     --   --  3    3   --   3   3                           Example 67 1      0     1    3   --   3   --   3   3                           Untreated  0      0     0    0   0    0   0    0   0                           Comparison                                                                     Imazamethabenz                                                                            3      2     2    2   3    3   3    3   3                           ______________________________________                                     

We claim:
 1. A herbicidal composition which comprises a compound of formula I ##STR14## in which A is one of the groups --CO--OR¹, --CO--NR⁶ R⁷ or --C≡N,R¹ is hydrogen, C₁ -C₁₂ -alkyl (optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, tri-C₁ -C₄ -alkylammoniumhalide, C₂ -C₅ -alkylenimino or di-C₁ -C₄ -alkylmethyleniminooxy), C₂ -C₁₂ -alkyl, interrupted by one or more oxygen or sulphur atoms and optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino, a C₃ -C₈ -alkenyl or C₃ -C₈ -alkynyl group (each of which is optionally substituted by C₃ -C₈ -alkoxy, phenyl or halogen), C₃ -C₈ -cycloalkyl, optionally substituted by methyl, di-C₁ -C₄ -alkylmethylenimino or C₃ -C₆ -cycloalkylenimino; R² and R³, which may be the same or different, are C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino or halogen; R⁴ is hydrogen, C₁ -C₁₀ -alkyl (optionally substituted by one or more of the same or different C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, halogen, phenyl or halophenyl), a C₂ -C₁₀ -alkenyl or C₂ -C₁₀ -alkynyl group (each of which is optionally substituted by one or more of the same or different C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, halogen or phenyl), or a C₃ -C₈ -cycloalkyl or C₄ -C₈ -cycloalkenyl group (each of which is optionally substituted by one or more of the same or different C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, trifluoromethyl, halogen or phenyl); R⁵ has the same meaning as R⁴ except hydrogen; or R⁴ and R⁵ together with the carbon to which they are attached form a C₃ -C₈ -cycloalkyl group; R⁶ and R⁷, which may be the same or different, are hydrogen or C₁ -C₄ -alkyl; X is methine, with the provisos, a) A is not --C≡N, when R⁴ and/or R⁵ are methyl or benzyl, and b) R¹ is not ethyl, when R⁴ is hydrogen and R⁵ is benzyl, as well as its alkali metal, alkaline earth metal, ammonium and organic ammonium salts, and their optically active isomers, in admixture with agricultural acceptable carriers or diluents.
 2. A method of combating weeds which comprises applying to the weeds r their locus a compound of formula I ##STR15## in which A is one of the groups --CO--OR¹, --CO--NR⁶ R⁷ or --C≡N,R¹ is hydrogen, C₁ -C₁₂ -alkyl (optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, tri-C₁ -C₄ -alkylammoniumhalide, C₂ -C₅ -alkylenimino or di-C₁ -C₄ -alkylmethyleniminooxy), C₂ -C₁₂ -alkyl, interrupted by one or more oxygen or sulphur atoms and optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino, a C₃ -C₈ -alkenyl or C₃ -C₈ -alkynyl group (each of which is optionally substituted by C₃ -C₈ -alkoxy, phenyl or halogen), C₃ -C₈ -cycloalkyl, optionally substituted by methyl, di-C₁ -C₄ -alkylmethylenimino or C₃ -C₆ -cycloalkylenimino; R² and R³, which may be the same or different, are C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino or halogen; R⁴ is hydrogen, C₁ -C₁₀ -alkyl (optionally substituted by one or more of the same or different C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, halogen, phenyl or halophenyl), a C₂ -C₁₀ -alkenyl or C₂ -C₁₀ -alkynyl group (each of which is optionally substituted by one or more of the same or different C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, halogen or phenyl), or a C₃ -C₈ -cycloalkyl or C₄ -C₈ -cycloalkenyl group (each of which is optionally substituted by one or more of the same or different C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, nitro, trifluoromethyl, halogen or phenyl); R⁵ has the same meaning as R⁴ except hydrogen; or R⁴ and R⁵ together with the carbon to which they are attached form a C₃ -C₈ -cycloalkyl group; R⁶ and R⁷, which may be the same or different, are hydrogen or C₁ -C₄ -alkyl; X is methine, with the provisos, a) A is not --C≡N, when R⁴ and/or R⁵ are methyl or benzyl, and b) R¹ is not ethyl, when R⁴ is hydrogen and R⁵ is benzyl, as well as its alkali metal, alkaline earth metal, ammonium and organic ammonium salts, and their optically active isomers.
 3. A derivative according to claim 1 in which R¹ is hydrogen, C₁ -C₁₂ -alkyl optionally substituted by di-C₁ -C₄ -alkylmethylenimino or di-C₁ -C₄ -alkylmethylenimino.
 4. A derivative according to claim 3 in which and any alkyl group in R¹ contains 1 or 2 carbon atoms.
 5. A derivative according to claim 1 in which R¹ is hydrogen, methyl, ethyl, dimethylmethylenimino or --(CH₂)₂ ON═C(CH₃)₂ and R⁵ is ethyl, propyl, isopropyl, CH(CH₃)CH₂ CH₃ or cyclohexyl.
 6. A derivative according to claim 5 in which R¹ is hydrogen.
 7. A herbicidal composition according to claim 1, in which R² and R³ are C₁₋₄ alkoxy, R⁴ is hydrogen and A is --CO--OR¹.
 8. A herbicidal composition according to claim 7, in which R¹ is hydrogen, C₁₋₁₂ -alkyl optionally substituted by di-C₁ -C₄ -alkylmethylenimino or di-C₁ -C₄ -alkylmethylenimino and R⁵ is C₁ -C₁₀ -alkyl or C₃ -C₈ -cycloalkyl.
 9. A herbicidal composition according to claim 8, in which R² and R³ are methoxy and any alkyl group in R¹ contains 1 or 2 carbon atoms and R⁵ contains 2 to 6 carbon atoms.
 10. A herbicidal composition according to claim 9, in which R¹ is hydrogen, methyl, ethyl, dimethylenimino or --(CH₂)₂ ON═C(CH₃)₂ and R⁵ is ethyl, propyl, isopropyl, CH(CH₃)CH₂ CH₃ or cyclohexyl.
 11. A herbicidal composition according to claim 10, in which R¹ is hydrogen an R⁵ is isopropyl.
 12. A method of combating weeds which comprises applying to the weeds or their locus a herbicidally effective amount of a compound according to claim 2 in which R² and R³ are C₁₋₄ alkoxy, R⁴ is hydrogen and A is --CO--OR¹.
 13. A method of combating weeds which comprises applying to the weeds or their locus a herbicidally effective amount of a compound according to claim 12 in which R¹ is hydrogen, C₁₋₁₂ alkyl optionally substituted by di-C₁ -C₄ -alkylmethylenimino or di-C₁ -C₄ -alkylmethylenimino and R⁵ is C₁ -C₁₀ -alkyl or C₃ -C₈ -cycloalkyl.
 14. A method of combating weeds which comprises applying to the weeds or their locus a herbicidally effective amount of a compound according to claim 13 in which R² and R³ are methoxy and any alkyl group in R¹ contains 1 or 2 carbon atoms and R⁵ contains 2 to 6 carbon atoms.
 15. A method of combating weeds which comprises applying to the weeds or their locus a herbicidally effective amount of a compound according to claim 14 in which R¹ is hydrogen, methyl, ethyl, dimethylenimino or --(CH₂)₂ ON═C(CH₃)₂ and R⁵ is ethyl, propyl, isopropyl, (CH(CH₃)CH₂ CH₃ or cyclohexyl.
 16. A method of combating weeds which comprises applying to the weeds or their locus a herbicidally effective amount of a compound according to claim 15 in which R¹ is hydrogen and R⁵ is isopropyl.
 17. Substituted 2-pyrimidinyl acetic acid derivative of the formula ##STR16## in which R¹ is hydrogen, C₁ -C₁₂ -alkyl (optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, tri-C₁ -C₄ -alkylammoniumhalide, C₂ -C₅ -alkylenimino or di-C₁ -C₄ -alkylmethyleniminooxy), C₂ -C₁₂ -alkyl, interrupted by one or more oxygen or sulphur atoms and optionally substituted by hydroxy, halogen, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₃ -C₆ -cycloalkyl, benzyl, furyl, tetrahydrofuryl, phenyl, halophenyl, C₁ -C₄ -alkylphenyl, C₁ -C₄ -alkoxyphenyl, nitrophenyl, cyano, carboxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino, a C₃ -C₈ -alkenyl or C₃ -C₈ -alkynyl group (each of which is optionally substituted by C₃ -C₈ -alkoxy, phenyl or halogen), C₃ -C₈ -cycloalkyl, optionally substituted by methyl, di-C₁ -C₄ -alkylmethylenimino or C₃ -C₆ -cycloalkylenimino;R⁵ is isopropyl, and its alkaline metal, alkaline earth metal, ammonium and organic ammonium salts and the optically active isomers thereof. 